Reaction product of hexamethylenetetramin and phenolic bodies and method of making same.



citizen of the United UNITED STATES PATENT OFFICE.

LEO H.

. comrANY, or NEW IBAEKELAND, or YONKERS, NEW YORK, ASSIGNOR r0 GENERALBAKELI'rE YORK, N. Y., A CORPORATION OF NEW YORK.

REACTION PRODUCT 0F HEXAMETHYLENETETRAMIN AND PHENOLIC BODIES AND METHODOF MAKING SAME. l

No Drawing.

To all whom it may concern:

I Be it known that I, LEO H. BAEKELAND, a States, residing at Yonkers,in the county of Westchester and State of New York, have inventedcertain new ,and' useful Improvements in Reaction Products ofHexamethylenetetramin and Phenolic Bodies and Methods of Making Same, ofwhich the following is a speclfication.

In my prior Patent No. 942,809, granted December 7, 1909, claimed amethod of preparing condensation products consisting in reacting on a'phe-' nolic body in presence of a base serving-as a condensing agent. Ihave further pointed out in the said patent that amins and amids, and ingeneral all derivatives of the type NH which possess basic propertiesare well adapted for use as condensing agents. have also in said patentexplained that ammonia, aqueous or anhydrous, may be employed, and thatit may by reaction with the formaldehyde, give rise tohexamethylenetetramin (CH,) N4, which'is to be regarded as the effectiveor activebasic condensing action be carried out agent. I have found thatunder certain conditions it is advantageous to employ previouslyprepared hexamethylenetetramin, or its phenolic addition products, orthe chemical equivalents of these bodies, as for example mixtures offormaldehyde and am monia in substantially the proportions required toyield hexamethylenetetramin; and that such use presents particularadvantages for the preparation of certain transparent or translucent,compact products having somewhat theappearance of amber, but readilydistinguishable therefrom by certain chemical characteristics, aftermore fully described. d

It is lmown that hexam'ethylenet'etr amm in presence of certain otherbodies decomposes by heat. It isknown also that hexamethylenetetraminforms co binations with phenol (see Beilsteins Hamdbuch der Organz'schenGhemie, 3rd edition, Vol. 11., page such compounds, special precautions,decompose with the disengagement of ammonia and other gaseous products,yielding a spongy mass of a solid material. I have found that if thelatter reunder certain special Specification of Letters Patent.

" with four parts by I have described and as hereinif heated withouteither to modify the technical Patented June 13, 1916.

Application filed December 13, 1910. Serial No. 597,072.

conditions, it becomes possible to obtain hard and infusible products oftechnical or com: mercial value. Products may thus be obtained which inappearance are very similar to amber, and which may be employed forpurposes similar to those for which amber is used, as well as for othertechnical applications. I find, for example, that if I boil together onepart of hexamethylenetetramin weight of phenol, and subject the productto further heating, I obtain a yellow, transparent, amber-like mass.

A compact mass will be obtained if the heating is effected underpressure, 'or if the heat be applied gradually, so that the ammonia setfree is retained in the mass. This result is facilitated by the presenceexcess of phenol above'the proportion required to convert intohexamethylenetetramintriphenol, or an other substances which may enterinto a solid solution in the mass and thereby facilitate the retentionof the ammonia.

The proportions above mentioned may be modified according to thepurposes in view;

of some the hexamethylenetetramin excess of the homologues of phenol orof for instance, the amount of phenol or other phenolic body may beincreased or diminished, and even if an excess of one or the other ofthe'reagents be used, such excess may to a certain extent be afterwardeliminated, either by evaporation or by other suitable means.

As above stated, phenolic bodies other than phenol may be used, as forexample the homologues of phenol and the hexameth ylenetetramin may bereplaced by any chemical bodies or mixtures of chemical bodies which areequivalent to hexameth- I ylenetetramin in their chemical action forthis process.

Inasmuch as the ultimate products of this reaction are similar to, ifnot identical with, certain insoluble, infusible condensation productsof phenols and formaldehyde prepared under special conditions,,it mightbe anticipated that with the mixture or combination ofhexamethylenetetramin and phenols, a certain amountof formaldehyde, orthe polymers of formaldehyde, could be used qualities of the finalproduct or to regulate the chemical p i ss tageous in certain cases.

and such addition is found advantins;

lents, I shall proceed to gether Instead of using hexamethylenetetraminin the pure or fully prepared condition, I may use mixtures offormaldehyde and ammonia, made directly or indirectly: for instance, Imay add ammonia to formaldehyde in suitable proportions, then add thephenolic body; or I may reverse the order of mixing, adding ammonia tothe phenolic body and then adding formaldehyde. The technical effectsare identical, which ever procedure be used.

Instead of formaldehyde, I may use substances, as for example OH G1,,which by reaction with ammonia yield hexamethylenetetramin. Instead ofammonia, I may use such ammonium salts, as for instance carbonate ofammonium, or such chemicals, as for instance carbamid, as ultimately mayreact with liberation of ammonia and are therefore chemically equivalentto ammonia in their action. Or again, instead of phenols, I may use,either in part or solely, an alcohol-phenol, such for example asoxybenzyl alcohol; or I may use any partial anhydrids of alcohol-phenolsalone with hexamethylenetetramin, or its equivalents, or. in conjunctionwith or addition to phenols and formaldehyde.

As is well understood in the art, such partial anhydrids ofphenol-alcohols are fusible, resinous bodies, or phenoliccondensaotherwise known as saliretins tlon products, or saliretinproducts; see Beilstein Hand- Okemz'e, third edibuclz. dew Orgcmis-ckention, Vol. II, page 1109, article Salirealso French Patent 350,180,British Patent 15,517 of 1905, and German Patent 189,262 to Fabriques deProduits de Chimie rganique de Iiaire, etc.).

After indicating as above some of the different ways in which my processmay be modified by substituting chemical equivadescribe two concreteexamples whereby the desired product may be obtained:

Example I: 25 grams hexamethylenetetramm, 110 grams phenol, 80grams-water. Boil together for about 50 minutes, then evaporate, andheat further until the product becomes hard.

Example II: 40 grams hexamethylenetetramlntriphenol, 85 grams phenol, 38grams formaldehyde (40% solution). Boil tofor ten minutes, thenevaporate to drive off water and other gaseous products, and then hardenby further heating.

The final heating may be rendered more effective by the use of increasedpressures, which permits the use of high temperatures.

For certain applications it may be found advantageous to add foreignsubstances to this material, such additions comprising either bodieswhich are insoluble in the mixture and act as fillers, as for instancefibrous or pulverulent materials as asbestos,

translucent or opaque wood fiber, lampblack, iron oxid, etc., or

such substances as resins, camphor, naphthalene, asphaltum, anthracene,etc., or other similar substances may be added which may form mixturesor solid solutions with the product. The addition of any such bodies asmentioned above may be useful for modifying specific properties of thematerial. In the same way, suitable catalytic agents or condensingagents as for example a small proportion of caustic soda may be addedfor the purpose of facilitating the reaction.

In its initial stages, and before the final application of heat whichproduces the maximum hardening, the product formed as above may forcertain purposes, as for instance the preparation of varnishes orpaints, be dissolved in alcohol or other ap propriate solvents; andthese solvents can be removed by evaporation before the substance issubmitted to the final heating for the purpose of hardening it.

In its final form, the reaction product is a poor conductor of heat andelectricity; it is vitreous in character and has usually a yellowishcolor, whicl may however vary according to the purity of the'materials,the temperature to which it has been subjected or according to itsdegree of oxidation. The product may be obtained'in transparent, massesaccording to the conditions of operation. Thus the presence in the massof residual water tends to render it opaque, whereas the presence of anexcess of a phenolic body or of other substances capable of formingsolid solutions tends to the formation of transparent products. It isinsoluble in ethyl alcohol, benzol, toluol, carbon disulfid andchloroform. It does not melt if heated, but heated at sufficiently hightemperatures, it is destroyed and chars without meltin Crushed orscraped, sawed or filed, or gently heated, it denotes the presence inthe interior of the mass of uncombined or loosely combined ammonia.Analysis shows the presence of total ammonia which may attain three tosix per cent. or somewhat more by weight of the product; the uncombinedor loosely combined ammonia may be'eliminated by sulficient heating.Submitted to dry distillation, it leaves a carbonized residue, andyields a distillate containing some water, some ammonia, some phenol-orhomologues of phenol, and Various other substances.

The amber-like appearance of the product is characteristic ofcondensation products produced in presence of ammonia, and the productis easily distinguished from those prepared with most other condensingagents of a basic character. For example, potash tends to yield productshaving a purplish shade, etc. i

The term "hexamethylenetetramin, as employed in the claims, is to beunderstood as including the chemical equivalents thereof, as for examplehomologues of hexamethylenetetramin, or mixtures of ammonia andformaldehyde, or other substances or mixtures which may engenderhexamethylenetetramin and are therefore equivalent thereto. Similarly,the word phenols is to be understood as including phenol, itshomologues, other phenolic bodies having an equivalent action ormixtures thereof. The expression uncombined ammonia is to be understoodas referring to ammonia which either exists in a free state in theproduct or is so loosely combined therein that it may be expelled bysimple application of heat without destructive distillation of theproduct, or dissolved out by treating the pulverized product with water.

I claim:

1. The method of producing compact yellow products having somewhat theappearance of amber and containing uncombined ammonia, which consists inreacting with phenols on hexamethylenetetramin under the influence ofheat, expelling a portion only of the liberated ammonia, andtransforming the reaction product into a compact infusible bodycontaining the residual ammonia.

2. The method of producing compact yellow products having somewhat theappearance of amber and containing uncombined ammonia, which consists inreacting with phenols on hexamethylenetetramin under the influence ofheat, expelling a portion only of the liberated ammonia, andtransforming the reaction product by the combined action of heat andpressure into a compact infusible body containing the residual ammonia.3. The method of producing hard and infusible phenolic condensationproducts, which consists in reacting on a phenolic body withhexamethylenetetramin in presence of water, heating to expel water andammonia, and then hardening the reaction product. 4. The method ofproducing hard and infusible phenolic condensation products, whichconsists in reacting on a phenolic body with hexamethylenetetramin inpres-- ence of Water, heating to expel water and ammonia, and thenhardening the reaction product by the combined action of heat andpressure.

5. The method of producing hard and infusible phenolic condensationproducts, which consists in reacting on a phenolic body withhexamethylenetetramin in pres- ,ence of water, heating to expel waterand a. portion only ofv the ammonia and then hardening the reactionproduct containing the residual ammonia;

G. The method of producing hard and infusible phenolic condensationproducts, which consists in reacting simultaneously on a phenolic bodywith hexamethylenetetramin and formaldehyde in presence of water,heating to expel Water and ammonia, and then hardening the reactionproduct.

7 The method of producing hard and in- .fusible phenolic condensationproducts, which consists in reacting simultaneously on a phenolic bodywith hexamethylenetetramin and formaldehyde in presence of water,heating to expel water and a portion only of the ammonia, and thenhardening the reaction product containing the residual ammonia.

8. As a new composition of matter, a hard, compact, homogeneous andinfusible phenolic condensation product characterized by its amber-likecolor, and by the presence ,therein of ammonia in proportion of at leastthree per cent. by weight of the product.

9. As a new composition of matter, a hard, compact, homogeneous andinfusible phenolic. condensation product characterized by its amber-likecolor, and by the presence therein of ammonia in excess of one-fifth ofthe equimolecular proportion of the phenolic body used.

' In testimony whereof, I affix my signature in presence of twowitnesses.

LEO H. BAEKELAND.

NVitnesses:

HERBERT S. MAY, W. S. GORDON, Jr.

